| Online-Ressource |
Verfasst von: | Sigmund, Lukas M. [VerfasserIn]  |
| Ehlert, Christopher [VerfasserIn]  |
| Enders, Markus [VerfasserIn]  |
| Graf, Jürgen [VerfasserIn]  |
| Gryn’ova, Ganna [VerfasserIn]  |
| Greb, Lutz [VerfasserIn]  |
Titel: | Dioxygen activation and pyrrole α-cleavage with calix(4)pyrrolato aluminates |
Titelzusatz: | enzyme model by structural constraint |
Verf.angabe: | Lukas Maximilian Sigmund, Christopher Ehlert, Markus Enders, Jürgen Graf, Ganna Gryn'ova, and Lutz Greb |
Jahr: | 2021 |
Umfang: | 9 S. |
Fussnoten: | First published: 06 May 2021 ; Gesehen am 29.11.2022 |
Titel Quelle: | Enthalten in: Angewandte Chemie. International edition |
Ort Quelle: | Weinheim : Wiley-VCH, 1998 |
Jahr Quelle: | 2021 |
Band/Heft Quelle: | 60(2021), 28, Seite 15632-15640 |
ISSN Quelle: | 1521-3773 |
Abstract: | The present work describes the reaction of triplet dioxygen with the porphyrinogenic calix[4]pyrrolato aluminates to alkylperoxido aluminates in high selectivity. Multiconfigurational quantum chemical computations disclose the mechanism for this spin-forbidden process. Despite a negligible spin-orbit coupling constant, the intersystem crossing (ISC) is facilitated by singlet and triplet state degeneracy and spin-vibronic coupling. The formed peroxides are stable toward external substrates but undergo an unprecedented oxidative pyrrole α-cleavage by ligand aromatization/dearomatization-initiated O−O σ-bond scission. A detailed comparison of the calix[4]pyrrolato aluminates with dioxygen-related enzymology provides insights into the ISC of metal- or cofactor-free enzymes. It substantiates the importance of structural constraint and element-ligand cooperativity for the functions of aerobic life. |
DOI: | doi:10.1002/anie.202104916 |
URL: | Volltext: https://doi.org/10.1002/anie.202104916 |
| Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202104916 |
| DOI: https://doi.org/10.1002/anie.202104916 |
Datenträger: | Online-Ressource |
Sprache: | eng |
Bibliogr. Hinweis: | Parallele Sprachausgabe : deutschSigmund, Lukas M.: Disauerstoffaktivierung und Pyrrol-α-Spaltung mit Calix[4]pyrrolatoaluminaten |
Sach-SW: | aluminum |
| dioxygen activation |
| intersystem crossing |
| metal-ligand cooperativity |
| structural constraint |
K10plus-PPN: | 182388802X |
Verknüpfungen: | → Zeitschrift |
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Lokale URL UB: | Zum Volltext |
Dioxygen activation and pyrrole α-cleavage with calix(4)pyrrolato aluminates / Sigmund, Lukas M. [VerfasserIn]; 2021 (Online-Ressource)